A282742 A7 B7 經濟部智慧財產局員工消費合作社印制衣 五、發明說明（I ) 本發明係有關於一種水和水性液體之吸收劑，該吸收 劑係基於水可溶脹，但不溶於水之聚合物，其中高矽含量 之沸石離子性地及/或由於機械包合地倂入。 商用的超吸收聚合物本質上爲交聯的聚丙烯酸，交聯 的澱粉-/丙烯酸接枝共聚物，交聯的水解澱粉/丙烯腈接 枝共聚物，交聯的聚（順丁烯二酸酐-共聚-異丁烯），或上 述之各種交聯聚合物之混合物，其中羧酸基已使用鈉及/ 或鉀離子部分中和。此類聚合物已發現可使用於衛生保健 製品來吸收體液，例如尿液或月經血，或在食品包裝方面 中做爲吸收墊，其中係藉由溶脹和形成水凝膠而用於吸收 大量的水性液體和體液，例如尿液或血液。此外，需在一 般用途壓力下滯留住所吸收的液體量。在超吸收聚合物的 技術進一步發展期間，這些產品所需達到的需求模式已在 近年間顯著地改變。 目前，超吸收體的發展已特別著重於與吸收之液體數 量和壓力穩定性相關。此類已交聯聚合產物係基於含有酸 基的單體且係得自於使用一或多種第一次交聯劑及/或一 或多種第二次交聯劑，並顯示出至目前仍無法達到的組合 性質，亦即高滯留性，在壓力下之高吸收性，低溶解性， 對液體迅速吸收，和在溶脹態下的高滲透性。當使用爲衛 生保健製品時，這些已交聯聚合產物所具有之優點爲一旦 經該聚合產物吸收後即可緊吸住流體，且不再與皮膚接觸 。因此可大幅地避免皮膚受損害，例如尿布疹。這種舒適 性甚至由於可吸收惡臭化合物而增加。 3 J-------------------訂---------線 ί ί (請先閱讀背面之注音3事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1282742 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（〆） 依據R0mpp Chemie Lexikon，尿液成分和惡臭化合物 的含量會隨生理性變化而改變；亦即特定物質所分泌的濃 度在整日期間會有所改變，因此不變的尿液組成中更準確 的數據係相對於俗稱之24小時尿液，依據健康成年人者則 含有尿素（平均20克），尿酸（0.5克），肌酸酐（1.2克） ’氨（〇·5克），胺基酸（2克），蛋白質（60毫克），少量 物質（0·5克，其中之大約70毫克爲D-葡萄糖或尿糖）， 檸檬酸（0.5克）和其他的有機酸，和一些維生素（C，Β12 等等）。亦存有下列的無機離子：Na+ ( 5.9克），Κ+ ( 2.7克 )’ NH/ ( 0.8 克），Ca2+ ( 0.5 克），Mg2+ ( 0.4 克）；C1· ( 8.9 克），P〇43· ( 4.1克），SCU2· ( 2.4克）。其中乾燥含量爲50 至72克之間。特別地，烷基呋喃，酮，內酮，吡咯，異硫 氰酸烯丙基酯，和二甲基碾已確認爲是尿液的揮發性成分 。大部份之揮發性成分係爲具有莫耳質量低於大約1000克 /莫耳且具有高蒸氣壓的分子。 尿液的揮發性成分亦已受到硏究，特別是A· Zlatkis 及其硏究同仁（Anal. Chem.卷45，763ff)。亦廣知者爲食 用蘆筍會造成人類尿液中含有機硫化合物的濃度增加（ R.H· Waring，Xenobiotika，卷 17，1363ff)。對於進行特定 飮食及/或攝取特定藥物的患者，或具有退化腎臟功能的 年長者，其尿液可能含有惡臭物質。罹患尿失禁的患者具 有增高分泌量的尿素酶，該尿素酶會將尿液中所含之尿素 轉換爲揮發性的毒性氨。同時，已廣知者爲病理性改變， 其稱之爲魚腥味徵候群。此係由於四級銨化合物的分泌增 4 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） -J------------------訂---------線 * J (請先閱讀背面之注音？事項再填寫本頁} 1282742 A7 __ B7 ___ 五、發明說明o ) (請先閱讀背面之注咅3事項再填寫本頁) 加。亦即，月經血可能會產生不佳的氣味。此氣味係由於 所分泌蛋白質受微生物分解時所生成。在月經血中的典型 異味物質以及血液成分分解後所產生的味道，與在尿液中 所生成成分之味道並無實質上的不同。在此案例中係有關 於具有莫耳重量低於1000克/莫耳的低分子量化合物。更 佳者，所述及者爲含氮雜環，例如毗咯，吡啶和其等之衍 生物。此外，亦會述及由食品釋出的味道，例如魚腥味（ 胺類）。 經濟部智慧財產局員工消費合作社印製 陰道分泌物和月經血的異味物質已受到G. Huggins和 G. Preti之硏究（臨床產科學和婦科學，卷24，2號，1981 年六月，355-377 )，其中發現具有分子量低於500克/莫 耳之低分子量物質。所特別提出之生成不悅氣味者爲脂肪 酸（例如丁酸，異戊酸）和一些芳香族化合物，例如毗啶 ，蚓哚和胸腺嘧啶。揮發性脂肪酸的數量會隨著月經週期 的時間階段改變（人類的陰道分泌物：揮發性脂肪酸含量 ，Richard P. Michael，R.W. Bonsall，Patricia Warner，科學 ，1974年十二月27日，1217-1219)。胺類並未在陰道分泌 物和月經血中發現。這是因爲健康女性的分泌物pH値爲 在酸性範圍內，於其中最多存有未具揮發性的銨鹽。只有 在病理條件下增高量的蛋白質受細菌分解轉換爲胺，如果 pH値同時增加時則便進入蒸氣域。 早先在失禁產品及女士衛生產品中所達到降低異味的 方法係基於減少游離氨的濃度。基本上，有二種方案來處 理：使用適當的尿素酶抑制劑來避免尿素降解而額外生成 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1282742 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（iV ) 氨（A. Norberg及其硏究同仁，老年學，1984，30，261ff )，或藉著將游離氨質子化且將之鍵結成爲羧酸銨鹽的形式 。此種方法實質上有其缺點，因爲僅有極少的氨和其他的 含氮化合物可受到控制。缺乏鹼基，例如硫醇，之惡臭化 合物仍然可以進入蒸氣域。 熟於此藝者已習知者爲沸石具有高度的吸收性質。 大部份的沸石係爲合成性化合物且包含氧化矽，氧化 鋁和多種金屬離子。它們的組成爲M2〇z · AhCb · xSiCh · yH2〇，其中M =單-或多價金屬，Η，錢等，z =原子價’ X =由1.8至約12，及y =由0至約8。結構性而言，沸 石的組成係由SiCU和A1CU四面體藉由氧橋相連，藉此形成 相同結構的通道系統和相同大小之互相連接腔。沸石之命 名係依據它們的孔隙口徑，例如沸石A (4.2 A)，沸石X (7.4 A)。當加熱時，大多數的沸石連續釋出所含的水’ 且不改變它們的晶體結構。依此方式，它們能夠調節其他 化合物，例如做爲催化劑或離子交換劑。此外，沸石藉由 合倂比格子通道系統中孔隙口徑更小截面的分子而顯示出 篩選效應。較大的分子因此被排除。在矽酸鋁結構中，陽 離子需要與A1CU四面體的負電荷平衡。 特別地，沸石的合成已廣泛地述於··沸石合成，ACS 論文集系列 398，Μ· L. Ocelli 和 Η· Ε· Robson 編輯（1989) 2-7頁。合成在結構中二氧化矽/氧化鋁比率爲>l〇〇，高 的水熱穩定性和對鹼性水溶液具有阻抗性之疏水性沸石已 揭示於專利申請案DE 195 32 500 A1。該等沸石所具有之顆 6 度適用中國國家標準（CNS)A4規格（210 X 297公釐） " " -Γ-------------------訂---------線 ··· (請先閱讀背面之注音？事項再填寫本頁) 1282742 A7 B7 經濟部智慧財產局員工消費合作社印制衣 五、發明說明（< ) 粒大小顯著地低於150微米。 專利文件US 4,795,482中教示疏水性沸石使用於降低 及避免有機氣味的用途。這種降低氣味的測量係使用液面 上空間之氣體色層分析法進行。 由專利申請案WO 91/12029和WO 91/12031中可知， 於US 4,795,482中所述及或以相似方式製得之疏水性沸石 可與超吸收體合倂使用，其中該沸石係『本質上地』與超 吸收體鍵結。由此得到之複合物可使用於衛生保健製品中 ，例如尿布或襯墊。該混合物之製備係在乾燥條件下混合 超吸收體和沸石。接著加入水，並觀察粒子的聚集作用（ W〇91/12031 )。在乾燥步驟之後，可將混合物倂至衛生保 健產品中。在專利申請案WO 91/12029中，沸石與黏合劑 共同分散於水中，及在塗覆製程中將之塗覆至超吸收體上 ，其中沸石之使用量爲相對於超吸收體之至少20%。 這兩種方法均有其缺點，因爲沸石物質與聚合物之鍵 結非常地弱，而且甚至當低的機械應力施加在複合物上時 會產生超吸收體和沸石的分離和分層。此種機械應力之產 生例如在運送超吸收體及/或包括超吸收聚合物的吸收劑 產品時。除分層之外，亦會產生處理極細粒子的問題。亦 及，當超吸收體使用可能含有黏合劑的水性分散液進行第 二次處理時，需預期可能產生超吸收體之結構及合倂的溶 脹性質之損壞。在超吸收體複合物中，高比率的非溶脹沸 石物質代表對性質模式的額外限制。 由專利申請案 EP 0,811，387 A1 和 EP 0,811，390 A1 中 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） Ί-------------------訂---------線 (請先閱讀背面之注音？事項再填寫本頁) 1282742 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（1；) 可知，具有二氧化矽/氧化鋁比率爲由1至5之沸石可使 用在襯墊中做爲氣味吸收劑。依據上述文件所製得之產品 已完成臨床試驗，並且所使用過的產品亦在嗅覺測試板中 經測試者評量。於上述專利申請案中所述及的乾燥混合物 極易產生分層。除此之外，於上述專利申請案中所需的沸 石數量極高，這對穿載衛生保健製品時的舒適性上爲不利 的效應。 因此本發明之目的爲提供一種能夠吸收水和水性液體 之聚合物，該聚合物具有一物質可鍵結例如由尿液或由身 體分泌出的其他流體之惡臭有機化合物，及其中 -其使用期間顯著降低所釋出之惡臭物質進入蒸氣域； -在吸收劑中存有實質上均勻分佈的芳香劑物質； -儘可能避免在前案條件中及使用期間的分層； --吸收劑在壓力下具有良好的滞留性質和溶脹性質；及 -使用儘可能低數量的芳香劑物質而確實達到芳香劑改性 〇 本發明之目的爲提供一種製造該除臭吸收劑聚合物的 方法，其中 -特別地避免混合粒度上實質不同的乾燥物質，例如顆粒 和粉末，所產生之困擾； -不產生粉塵；及 --在製備期間避免產生微粒的聚集作用。 依據本發明，該目的之達成係藉由由已交聯，單烯系 不飽和化，攜有酸基之部份中和單體組成吸收劑聚合物， 8 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） " '~' " Ί-------------------訂---------線· (請先閱讀背面之注意事項再填寫本頁) 1282742 A7 經濟部智慧財產局員工消費合作社印製 B7 五、發明說明（7 ) 該聚合物具有單獨或混合的α，3,7，5-環糊精或其衍生物 ，和高矽含量沸石以離子性，共價性或機械方式鍵結或合 倂。 於本發明意義中『高砂含量』（high in silicon)意爲二 氧化矽/氧化鋁之比率爲> 1〇，較佳爲>20，更佳爲>50 ，且甚至更佳爲>1〇〇。二氧化矽/氧化鋁之比率爲>5〇〇 時爲特別佳者。 於本發明意義中『已交聯』意爲聚合物已交聯及/或 已表面交聯。 使用於本發明之沸石爲去鋁，疏水性（親油性）的沸 石變體，在其結構中具有二氧化矽/氧化鋁比率爲> 10， 較佳爲> 20，更佳爲> 50，及特別佳者爲> 100。最爲佳者 爲二氧化矽/氧化鋁比率爲> 500。所使用之數量爲相對於 吸收劑總數量之0.0M0重量％，較佳爲0.1-5重量％，及 更佳爲0.70-3重量％。此類沸石例如爲由Degussa AG所售 且商品名爲Flavith®或由U〇P所售之商品Alscents®。 Flavith®之鑑定更詳盡地列於KC-CZ 42-1-05-1098 T&D產品 資料表中。該產品資料表藉此倂於本文以爲參考，因此提 及所揭示的其中一部分。 可使用各種不同的方法對本發明中具有選用超吸收劑 性質之聚合物進行聚合作用，例如本體聚合作用，溶液聚 合作用，噴霧聚合作用，逆乳化聚合作用，及逆分散化聚 合作用。較佳者，使用水爲溶劑來進行溶液聚合作用。溶 液聚合作用亦可使用連續或批次方式進行。在專利文獻中 私紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐 -7-------------------訂---------線 (請先閱讀背面之注咅？事項再填寫本頁) A7 1282742 ___B7___ 五、發明說明（3 ) 包括了與濃度條件，溫度，起始劑和第二次催化劑之類型 和數量相關的廣範圍可能變化。典型的方法已述於下列的 專利說明書中：US 4,286,082 ; DE 27 06 135，US 4,076,663 ，DE 35 03 458，DE 40 20 780，DE 42 44 548，DE 43 23 001，DE 43 33 056，DE 44 18 818。該等揭示藉此倂於本文 以爲參考，因此提及所揭示的其中一部分。 使用於本發明之含不飽和酸基單體例如爲丙烯酸，甲 基丙烯酸，巴豆酸，異巴豆酸，順丁烯二酸，反丁烯二酸 ，衣康酸，乙烯基乙酸，乙烯基磺酸，甲基烯丙基磺酸， 2-丙烯醯胺基-2-甲基小丙基磺酸，以及鹼及/或銨鹽。較 佳者爲使用丙烯酸及其鹼及/或銨鹽，及其等之混合物。 此外，亦可能在與例如腈基進行聚合作用之前的最後可能 階段將單體水解爲酸基。 爲了改變聚合物性質，在水性聚合作用批次中可溶解 至多30重量％之其他共單體，例如丙烯醯胺，甲基丙烯醯 胺，丙烯腈，（甲基)烯丙基醇乙氧基化物，和可選用醇或 乙氧基化物之單（甲基)丙烯酸酯。 在分子中具有多於一個反應性基的小量交聯單體可與 上述之單體共聚合，藉此形成不再溶於水而僅溶脹之部份 交聯聚合產物。雙-或多功能單體，例如醯胺類如亞甲基雙 丙烯基-或-甲基丙烯醯胺，或亞乙基雙丙烯醯胺可做爲交 聯單體，亦及，烯丙基化合物如（甲基)丙烯酸烯丙基酯， 較佳爲與1至30莫耳烷氧乙烷反應之烷氧化(甲基)丙烯酸 烯丙基酯，氰腺酸三烯丙基酯，順丁烯二酸二烯丙基酯， 10 本^氏張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱)"" " Ί-------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 1282742 Α7 五、發明說明（) 聚烯丙基酯，四烯丙基氧基乙烷，三烯丙基胺，四烯丙基 亞乙基二胺，磷酸或亞磷酸的烯丙基酯，以及可交單體如 未讎麵如甲基丙嫌酸胺或丙讎胺和由其等衍生出之 醚之N·經甲基化合物，以及多元醇和院氧化多元醇的酯類 ，例如一丙烯酸酯或三丙烯酸酯，如二丙烯酸丁二醇或乙 二醇酯，聚二（甲基)丙烯酸乙二醇酯，三丙烯酸三羥甲基 丙基酯，較讎與1至30莫耳院氧乙院進行氧基院基化( 乙氧化）之二羥甲基丙基之二_及三丙烯酸酯，甘油醇和季 戊四醇以及較佳爲與1至30莫耳烷氧乙烷進行氧基乙基化 之甘油醇和季戊四醇的丙烯酸酯和甲基丙烯酸酯。較佳爲 使用三稀丙基胺，多元醇或其等烷氧化物的丙烯酸酯，及 丙烯酸甲基烯丙基醇酯或其等之烷氧化物。交聯單體的比 率爲相對於總單體之由0.01至3.0重量％，較佳爲由0.05 至2.0重量％，及最佳爲由〇 〇5至ι·5重量％。 該等酸性單體較佳爲進行中和作用。中和作用可使用 各種不同的方式進行。依據US 4,654,039的教示，該聚合 作用一方面可直接與酸性單體進行，接著在聚合物凝膠中 進行中和作用。該專利說明書藉此倂於本文以爲參考，因 此提及所揭示的其中一部分。另一方面且爲較佳者，在進 行聚合作用之前將酸性單體成分中和至20-95%，較佳爲 50-80%，在該案例下，當聚合作用開始進行之當時其等係 以鈉及/或鉀鹽及/或銨鹽形式存在。較佳爲使用對接著 之聚合作用不具不利效應之鹼進行中和作用。較佳爲使用 氫氧化鈉或氫氧化鉀溶液及/或氨，其中氫氧化鈉溶液爲 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） J.-------------------訂---------線 (請先閱讀背面之注音？事項再填寫本頁) 1282742 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（) 特別佳者；依據us 5,314,420和US 5，154,713中所教示者 ’加入碳酸鈉，碳酸鉀或碳酸氫鈉具有額外的正面效應。 在起始該絕熱溶液聚合作用的聚合作用之前，將部份中和 的單體溶液冷卻至3(TC以下之溫度，較佳爲低於20°C。這 些專利說明書藉此倂於本文以爲參考，因此提及所揭示的 其中一部分。在另一個所提及之方法中，其他的溫度依據 此技藝中所述者爲習知且習用者。 本發明的聚合產物可能含有至多40重量％之水溶性 聚合物做爲基質進行接枝作用。特別者，這些包括部份或 完全皂化的聚乙烯醇，澱粉或澱粉衍生物，纖維素或纖維 素衍生物，聚丙烯酸，聚乙二醇類，或上述之混合物。加 入做爲接枝作用基質之聚合物之分子量必需配合聚合物作 用條件的環境。例如，在一個水溶液聚合作用的案例下， 爲了黏度的理由其可能需要使用低或中度分子量之聚合物 ，然而這種因素在懸浮液聚合作用中僅扮演較小的角色。 除了部份中和丙烯酸進行交聯聚合作用而得到的聚合 物之外’其等較佳爲使用額外含有經接枝聚合之澱粉，或 聚乙烯醇的成分。 本發明的聚合作用方法可使用各種不同條件起始。例 如使用放射性，電磁性或紫外性幅射來照射，或使用二個 化合物的氧化還原反應，例如亞硫酸氫鈉與過硫酸鉀作用 ，或抗壞血酸與過氧化氫作用。亦可使用俗稱爲自由基起 始劑者做爲聚合作用之起始劑進行熱引致分解作用，該等 自由基起始劑例如爲偶氮二異丁腈，過氧化焦硫酸鈉，第 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） J--------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 1282742 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（丨丨） 三丁基氫過氧化物，或二苯甲醯基過氧化物。此外，亦可 使用上述方法的組合。 原則上，該等聚合產物可依據下列二種方法製備： 依據第一個方法，在水溶液中且存有交聯劑及選用聚 合物添加劑之下，藉由自由基聚合作用將部份中和的丙烯 酸轉化爲凝膠，接著將該凝膠壓碎且乾燥直至達到粉末化 ，可流動態，將之硏磨，且篩選成所需要的粒度。溶液聚 合作用可使用連續式或批次式進行。於專利文獻中可包括 與濃度條件，溫度，起始劑類型和數量有關的各種廣範圍 變異性，和選用第二次交聯作用的變異性。典型的方法已 述於下列之專利說明書中：US 4,076,663 ; US 4,286,082 ; DE 27 06 135，DE 35 03 458，DE 35 44 770，DE 40 20 780 ，DE 42 44 548，DE 43 23 0(U，DE 43 33 056，DE 44 18 818。該等檔案藉此倂於本文以爲參考，因此提及所揭示的 其中一部分。 逆懸浮液和乳液聚合作用的方法亦可使用來製備聚合 產物。在這些方法中，將一種水性，部份中和的丙烯酸溶 液利用保護性膠質物及/或乳化劑而分散於疏水性有機溶 劑中，及使用自由基起始劑起始聚合作用。交聯劑可溶解 於單體溶液中並且度量後共同加入，或分別加入，及選用 地隨後加入。選擇性存在的聚合性接枝基質係利用單體溶 液加入或直接置入油相中。後來，水由混合物中利用共沸 移除，且將聚合產物過濾及選擇性地壓碎，及乾燥至達到 粉末化，可流動態，硏磨及篩選至所需要的粒度。 13 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I--------------------tT---------^· (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 1282742 A7 B7 五、發明說明（\〆） 利用接下來的表面交聯方法，可改良本發明聚合產物 的性質模式，特別是在壓力下的液體吸收性，因此可避免 習見之『凝膠塊狀化』（gel blocking)現象’其中稍微溶脹 的聚合物粒子相互黏附，藉此在例如尿片中阻止進一步的 液體吸收和液體分配。在這種第二次交聯作用中’可使用 交聯劑，在提高的溫度下使聚合物分子的羧基在超吸收體 微粒的表面處交聯。第二次交聯的方法已在數種專利說明 書中述及，例如 DE 40 20 780，EP 317，106 和 W0 94/9043。 依據本發明，所有揭示於US 5,314,420，第8頁，第 3-45行之熟於本技藝者所習用的第二次交聯劑可有利地倂 用第一次交聯劑，或交聯劑之組合。上述之文獻藉此倂於 本文以爲參考，因此提及所揭示的其中一部分。通常，這 些化合物含有至少二個足以與羧酸或羧基反應的官能基。 醇，胺，醛，和碳酸鹽基爲較佳者，同時亦可使用具有不 同官能性之交聯劑分子。較佳者係使用多元醇，聚胺，聚 胺基醇，聚環氧化物，和碳酸亞烷基酯。特別地，可使用 下列之第二次交聯劑：乙二醇，二甘醇，三乙二醇，聚乙 二醇，甘油，聚甘油，丙二醇，二乙醇胺，三乙醇胺，聚 丙二醇’環氧乙烷和氧化丙烯的嵌段共聚物，山梨糖醇脂 肪酸酯，乙氧化山梨糖醇脂肪酸酯，三羥甲基丙烷，乙氧 化三羥甲基丙烷，季戊四醇，乙氧化季戊四醇，聚乙烯醇 ’山梨醣醇’碳酸亞乙基酯，碳酸亞丙基酯。特別佳者爲 使用多元醇和碳酸亞乙基酯做爲第二次交聯劑。第二次交 聯劑的使用數量爲相對於欲進行第二次交聯作用聚合物之 本紙張尺度適用中國國豕標準（CNS)A4規袼（210 X 297公釐） --------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 1282742 A7 _____B7_____ 五、發明說明（Ο ) 0.01至30重量％，較佳爲0.1-10重量％。 (請先閱讀背面之注咅？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 在第二次交聯作用之前，較佳爲先乾燥聚合物，硏磨 ，對所應用技術中所需的個別顆粒分級進行篩選，及接著 置入第二次交聯反應。然而，已証實在某些情況下，可有 利地在乾燥聚合物凝膠之前，或將部份或完全乾燥的聚合 物硏磨之前的更早階段，加入第二次交聯劑。本發明所使 用之第二次交聯作用已揭示於US 4,666,983和DE 40 20 780 。這些文獻藉此倂於本文以爲參考，因此提及所揭示的其 中一部分。有利者爲通常這些第二次交聯劑以水，有機溶 劑或上述混合物的溶液形式加入，特別是在這些案例中係 使用低數量的第二次交聯劑。使用來施加第二次交聯劑的 適當混合設備例如爲Patterson-Kelley混合器，DRAIS湍流 混合器，L5dige混合器，Ruberg混合器，螺旋混合器，轉 盤混合器，和流體-床混合器，和在高頻率下使用旋轉刀混 合粉末的連續操作垂直混合器（Schugi混合器）。一旦第二 次交聯劑與預先交聯之聚合物混合之後，加熱至溫度爲60 至250°C，較佳爲由135至200°C，及更佳由150至185°C ，因此可進行第二次交聯反應。額外加熱的時間階段則受 限於聚合產物所需的性質模式由於熱損壞而受到破壞的時 間。 依據所使用的類型而定，其可使用各種不同的篩選分 級來處理聚合產物，例如對尿片而言爲在100和1〇〇〇微米 之間，及較佳爲150和850微米之間。大體上，這種顆粒 分級係在第二次交聯作用之前及/或之後，利用硏磨和舖 15 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1282742 A7 B7 五、發明說明 --打碎，接著乾燥，硏磨； -選擇性地篩選；及 --表面交聯作用； 其中高矽含量沸石在最後的表面交聯作用期間加至聚合產 物中。 較佳者，高矽含量沸石之加入係在懸浮中。 於本發明意義中，『高矽含量』意爲二氧化矽/氧化 鋁之比率爲>10，較佳爲>20，更佳爲>50，且甚至更佳 爲>100。二氧化矽/氧化鋁之比率爲> 500時爲特別佳者 〇 所使用之沸石係爲在懸浮液中。較佳的液相爲水，但 是亦可使用水和有機溶劑的混合物。 依據本發明，沸石的加入可如同於下文中所述地，在 製造粉末化聚合產物的各種不同製程階段中進行。在水性 懸浮液中之沸石可在製備的製程步驟之前或期間加至聚合 產物中，因此此種異味吸收成分和聚合產物之間可達到特 別有效的鍵結。 在本發明方法的一假較佳具體實施例中，沸石係在聚 合作用之前，直接地加至單體水溶液中。當吸收劑係在懸 浮液聚合作用中產生時，其亦可能將在油相中的所有或部 份沸石預先荷電荷，並度量單體溶液。當只有一部份沸石 預先荷電荷時，其餘者可藉由單體溶液來加入。 在本發明方法的另一個較佳具體實施例中，沸石以在 水中或有機溶劑或兩者混合物中的懸浮液形式，施加至碎 17 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ---------訂--------線』 經濟部智慧財產局員工消費合作社印製 1282742 A7 經濟部智慧財產局員工消費合作社印製 B7 五、發明說明（\r[) 依據本發明，在加入高矽含量沸石之前’水含量需降 至低於10重量％。 較佳者，在加入高砂含量沸石之前’水含量需降至低 於30重量％，更佳爲不低於50重量％ ’及甚至更佳者爲 並不低於65重量％。 將沸石加至聚合產物時較佳係利用懸浮液。 使用本發明方法時’當沸石倂至合成性聚合物可製得 吸收劑聚合物時，甚至在施加機械應力之後’例如在95 rpm的球磨機中6分鐘’沸石並未由聚合產物中完全移除 。於本發明方法中，在施加此種應力之後，低於80%，及 通常爲40-60%，之倂至聚合產物中的沸石總數量被移除。 相較於未含有沸石的粉末化吸收劑，本發明的聚合產 物顯示出對惡臭化合物改良吸收性。 聚合產物中，發現用在例如衛生保健製品且可吸收例 如尿液之體液，或包裝領域如肉和魚產品時，它們均可利 用溶脹作用且形成水凝膠而吸收大量的水性液體和體液， 例如尿液，血液，或肉汁。因此，本發明亦有關於此種用 途。 本發明的聚合產物可做爲粉末結構來吸收液體，或預 先固定在發泡或未發泡沬片狀材料中。例如，用於吸收液 體的構造爲嬰兒的尿片，失禁製品，或在食品中置入包裝 單兀中的吸收劑。在本發明的吸收劑聚合產物中，沸石對 聚合物的鍵結力即使在機械應力之下，例如運輸該吸收劑 聚合產物時，仍極爲強大，因此聚合物與沸石並不會產生 19 本紙張尺度_ + @國家標準（CNS)A4規格（21G X 297公爱） ^----------—--------訂---------線 (請先閱讀背面之注音？事項再填寫本頁) 1282742 A7 經濟部智慧財產局員工消費合作社印製 Β7 五、發明說明（0) 實質的分離和分層’而且特別地是並不會產生處理極細粒 子的問題。 進一步處理本發明的聚合產物爲較有利’因爲依據前 案，並無法達到超吸收體和沸石，特別是少量沸石，的分 離和均勻配料。本發明之聚合產物，則可簡易地配料，確 使在吸收劑產品中，例如襯墊’含有一定濃度具有超吸收 劑性質的聚合產物和芳香劑成分。 更甚者，經發現本發明吸收劑特別優良地適合倂入活 性物質。敏感活性物質’例如與氧化降解有關者，其等之 穩定性可在倂至本發明吸收劑後得到實質的改良。 此外，本發明的聚合產物可使用於植物培育，及在農 業中用於控制有害生物。在植物培育方面，與植物根部相 鄰的聚合產物可充份地供給液體及預先加入的營養物，及 其能夠在延長的時間階段下同時儲存且釋出。 在有害生物控制方面，聚合產物可加入單一的活性物 質或多種活性物質的組合’其係用於依時間和數量的控希u 方式釋出。 本發明將於下列實施例中說明。但這些例證僅經由實 施例陳述並非限定本發明的一般觀念。 下文中將解釋本發明聚合產物的製造和性質。此外， 亦將述及決定具有超吸收劑性質聚合物的性質測試方法和 步驟。 測試方法 測試方法1 :使用茶袋方法測定滯留性，並且以三次測摄 20 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） I---------------------IT---------^· (請先閲讀背面之注咅？事項再填寫本頁) 1282742 A7 B7 五、發明說明ο/) (請先閱讀背面之注意事項再填寫本頁) 的平均値表示。大約200毫克的聚合產物加至茶袋中並且 浸在〇.9%NaCl溶液中30分鐘。接著將茶袋置於離心機中 (直徑裡23公分，1400 rpm)離心3分鐘，及稱重。使用 未含有吸收水聚合物的茶袋做爲空白實驗。 滯留性=最終重量-空白實驗/起始重量 [g/g] 測試方法2 :在壓力下之液體吸收性（AAP測試，EP 0,339,461 ) 在壓力下（壓力負載50 g/cm2)的吸收性係依據在EP 0,339,461，第7頁中所述的方法測定。該文獻藉此倂於本 文以爲參考，因此提及所揭示的其中一部分。將大約0.9 克之超吸收體置於具有篩網底部的圓柱體中稱重。均勻分 佈的超吸收體層載入釋出50 g/cm2壓力的活塞。然後已預 先稱重的圓柱體置於一玻璃過濾板上且放入含有〇.9%NaCl 溶液淺盤中，過濾板的高度準確地液面相同。在圓柱體單 元吸收0.9%NaCl溶液1小時後，再重新稱重，並依據下 列計算AAP : 經濟部智慧財產局員工消費合作社印制衣 AAP=最終重量（圓柱體單元+超吸收體）一起始重量（ 圓柱體單元+浸漬後超吸收體）/超吸收體之起始重量 測試方法3:惡臭化合物吸收性的測定 〇·1克粉狀吸收劑加至2毫升惡臭化合物的水溶液（ 包括5重量％乙醇），並密封在5毫升測試容器中。將其置 於23°C下12小時，使用液面上空間GC，相對於一個空白 測驗定量測量液體上蒸氣域中的惡臭化合物含量。 測試方法4:吸收劑聚合物的矽含量測定係藉由將矽酸鹽 21 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 1282742 Δ7 Α7 Β7 五、發明說明（y°) 反應成鉬藍，接著進行光度分析。預先地，矽已使用鹼分 解作用定量反應成爲砂酸鹽（Photometrische Analyse，編輯 :Β· Lange，Zdenek L，Vejdelek S.，1987 年版，383 頁， VCH)。 實施例： 賁施例la 該實施例說明製備具有超吸收劑性質之聚合物凝膠。 預備1300克之丙烯酸，2115.9克之蒸餾水，2.7克之 聚丙烯酸乙二醇單烯丙基醚酯，及1.25克之聚二丙烯酸乙 二醇酯溶液。使用899.10克之50%氫氧化鈉溶液，利用攪 拌進行部分中和作用（中和作用程度（DN): 60%)，冷卻 。溶液冷卻至7-8°C，以氮通氣大約20分鐘。然後，加入 溶解於22.5克蒸餾水中之0.45克偶氮雙(2-脒基丙烷）二氫 氯酸鹽，溶解於25克蒸餾水中之1.35克過氧化焦硫酸鈉 ，及溶解於22.5克蒸餾水中之0.315克過氧化氫（35% )。 後來，聚合作用藉由加入溶解於9克水中之0.0675克抗壞 血酸來起始，其間產生溫度顯著地提高。得到一種似凝膠 產物，進一步的處理將於下文中之實施例述及。 實施例lb 該實施例說明製備另一種具有超吸收劑性質之聚合物 凝膠。 預備1300克之丙烯酸，2015.9克之蒸餾水，6·5克之 聚丙烯酸乙二醇單烯丙基醚酯，及3.9克之聚二丙烯酸乙 二醇酯溶液。使用997.10克之50%氫氧化鈉溶液’利用攪 22 *5^尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐^ I--------------------訂---------線 41^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 1282742 A7 B7 五、發明說明（>4 ) 拌進行部分中和作用（DN= 70%)，冷卻。溶液冷卻至7-8 °C，以氮通氣大約20分鐘。然後，加入溶解於22·5克蒸 餾水中之0.45克偶氮雙(2-脒基丙烷）二氫氯酸鹽，溶解於 25克蒸餾水中之1.35克過氧化焦硫酸鈉，及溶解於22.5 克蒸餾水中之0.315克過氧化氫（35%)。後來，聚合作用 藉由加入溶解於9克水中之0.0675克抗壞血酸來起始，其 間產生溫度顯著地提高。得到一種似凝膠產物，進一步的 處理將於下文中之實施例述及。 實施例lc 該實施例說明製備另一種具有超吸收劑性質之聚合物 凝膠。 預備1300克之丙烯酸，2017.19克之蒸餾水，及做爲 交聯劑之3.9克三烯丙基胺溶液。使用997.10克之50%氫 氧化鈉溶液，利用攪拌進行部分中和作用（ DN= 70% )， 冷卻。溶液冷卻至7-8°C，以氮通氣大約20分鐘。然後， 加入溶解於22.5克蒸餾水中之0.45克偶氮雙(2-胖基丙烷） 二氫氯酸鹽，溶解於25克蒸餾水中之L35克過氧化焦硫 酸鈉，及溶解於22.5克蒸餾水中之0.315克過氧化氫（35 %)。後來，聚合作用藉由加入溶解於9克水中之0.0675 克抗壞血酸來起始，其間產生溫度顯著地提高。得到一種 似凝膠產物，進一步的處理將於下文中之實施例述及。 實施例2 將500克得自於實施例lb-c中之凝膠打碎且均勻灑佈於依 據在下表中所示數量的Flavith® S108 (Degussa AG， 23 (請先閱讀背面之注意事項再填寫本頁) ----11--訂---II--I 一 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） 實施例 滞留性 [g/g] Flavith S108 wt.-% Flavith D wt-% 沸石A wt.-% 2a 32.5* 1 0 0 2b 32.5* 2 0 0 2c 33.0* 0 1 0 2d 33.0* 0 2 0 2e* 31.0# 0 0 1 2f** 30.8# 0 0 2 1282742 A7 B7 五、發明說明（〆）A282742 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printing Clothing V. Invention Description (I) The present invention relates to an absorbent for water and an aqueous liquid which is based on water swellable but insoluble in water. The sorghum content of the zeolite is ionic and/or intrusive due to mechanical inclusion. Commercial superabsorbent polymers are essentially crosslinked polyacrylic acid, crosslinked starch-/acrylic graft copolymers, crosslinked hydrolyzed starch/acrylonitrile graft copolymers, crosslinked poly(maleic anhydride) a copolymerized-isobutylene, or a mixture of the various crosslinked polymers described above, wherein the carboxylic acid group has been partially neutralized with sodium and/or potassium ions. Such polymers have been found to be useful in health care products for absorbing body fluids, such as urine or menstrual blood, or as absorbent pads in food packaging, where they are used to absorb large amounts by swelling and forming hydrogels. Aqueous liquids and body fluids such as urine or blood. In addition, the amount of liquid absorbed is retained under normal use pressure. During the further development of technology for superabsorbent polymers, the demand patterns required for these products have changed significantly in recent years. At present, the development of superabsorbents has been particularly focused on the amount of liquid absorbed and pressure stability. Such crosslinked polymeric products are based on monomers containing acid groups and are derived from the use of one or more first crosslinking agents and/or one or more second crosslinking agents, and have been shown to be The combined properties achieved, namely high retention, high absorbency under pressure, low solubility, rapid absorption of liquids, and high permeability in the swollen state. When used as a sanitary care product, these crosslinked polymeric products have the advantage that once absorbed by the polymeric product, the fluid can be held tightly and no longer in contact with the skin. Therefore, the skin can be largely prevented from being damaged, such as diaper rash. This comfort is increased even by the absorption of malodorous compounds. 3 J-------------------Book --------- Line ί ί (Please read the phonetic 3 on the back and fill out this page) Paper The scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1282742 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Invention description (〆) According to R0mpp Chemie Lexikon, urine composition and malodorous compound content It will change with physiological changes; that is, the concentration secreted by a particular substance will change throughout the day, so the more accurate data in the constant urine composition is relative to the commonly known 24-hour urine, based on healthy adulthood. The person contains urea (average 20 grams), uric acid (0.5 grams), creatinine (1.2 grams) 'ammonia (〇 · 5 grams), amino acids (2 grams), protein (60 mg), a small amount of substances (0 • 5 grams, of which about 70 mg is D-glucose or urine sugar), citric acid (0.5 grams) and other organic acids, and some vitamins (C, Β12, etc.). The following inorganic ions are also present: Na+ (5.9 g), Κ+ (2.7 g) 'NH/ (0.8 g), Ca2+ (0.5 g), Mg2+ (0.4 g); C1· (8.9 g), P〇43 · (4.1 g), SCU2· (2.4 g). The dry content is between 50 and 72 grams. In particular, alkylfurans, ketones, lactones, pyrrole, allyl isothiocyanate, and dimethyl milling have been identified as volatile constituents of urine. Most of the volatile components are molecules having a molar mass of less than about 1000 g/mole and a high vapor pressure. The volatile components of urine have also been studied, especially A. Zlatkis and his colleagues (Anal. Chem., Vol. 45, 763ff). It is also known that eating asparagus causes an increase in the concentration of organic sulfur compounds in human urine (R.H. Waring, Xenobiotika, Vol. 17, 1363ff). For patients who have a specific foraging and/or ingestion of a specific drug, or an elderly person with degenerative kidney function, the urine may contain malodorous substances. Patients with urinary incontinence have a high secretion of urease, which converts the urea contained in the urine into volatile toxic ammonia. At the same time, it is well known that pathological changes are called fishy smell syndromes. This is due to the increase in the secretion of quaternary ammonium compounds. 4 This paper scale applies to the Chinese National Standard (CNS) A4 specification (21〇X 297 mm) -J----------------- -Book---------Line* J (Please read the phonetic on the back? Please fill out this page again) 1282742 A7 __ B7 ___ V. Invention description o ) (Please read the note on the back 咅 3 items before Fill in this page) Plus. That is, menstrual blood may produce a bad smell. This odor is generated when the secreted protein is decomposed by microorganisms. The typical odorous substance in the menstrual blood and the taste produced by the decomposition of the blood component are not substantially different from the taste of the component produced in the urine. In this case it is related to low molecular weight compounds having a molar weight of less than 1000 g/mole. More preferably, the compounds are nitrogen-containing heterocycles such as pyrrol, pyridine and the like. In addition, the taste released from food, such as fishy smell (amines), will also be mentioned. The odor substances of vaginal secretions and menstrual blood printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs have been studied by G. Huggins and G. Preti (Clinical Obstetrics and Gynecology, Vol. 24, No. 2, June 1981, 355-377) wherein a low molecular weight material having a molecular weight of less than 500 g/mole was found. Particularly preferred to produce unpleasant odors are fatty acids (e.g., butyric acid, isovaleric acid) and aromatic compounds such as pyridine, guanidine and thymine. The amount of volatile fatty acids changes with the time period of the menstrual cycle (human vaginal secretions: volatile fatty acid content, Richard P. Michael, RW Bonsall, Patricia Warner, Science, December 27, 1974, 1217-1219 ). Amines are not found in vaginal secretions and menstrual blood. This is because the secretion pH of healthy women is in the acidic range, and there are at most unvolatile ammonium salts. Only the increased amount of protein under pathological conditions is converted to an amine by bacterial decomposition, and if the pH 値 increases simultaneously, it enters the vapor domain. The method of reducing odors previously achieved in incontinence products and women's hygiene products is based on reducing the concentration of free ammonia. Basically, there are two options to deal with: use the appropriate urease inhibitor to avoid urea degradation and generate an additional 5 paper sizes for the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1282742 A7 B7 Ministry of Economics Property Bureau employee consumption cooperatives printed five, invention instructions (iV) ammonia (A. Norberg and his colleagues, gerontology, 1984, 30, 261ff), or by protonation of free ammonia and bonding it to carboxy The form of the ammonium salt. This approach has its drawbacks essentially because only very little ammonia and other nitrogen-containing compounds can be controlled. Lack of bases, such as mercaptans, can still enter the vapor domain. It is well known to those skilled in the art that zeolites have a high absorption property. Most zeolites are synthetic compounds and contain cerium oxide, aluminum oxide and various metal ions. Their composition is M2〇z · AhCb · xSiCh · yH2〇, where M = mono- or polyvalent metals, ruthenium, money, etc., z = valence valence 'X = from 1.8 to about 12, and y = from 0 to about 8. Structurally, the composition of the zeolite consists of a SiCU and an A1CU tetrahedron connected by an oxygen bridge, thereby forming a channel system of the same structure and interconnecting cavities of the same size. Zeolites are named according to their pore size, such as zeolite A (4.2 A) and zeolite X (7.4 A). When heated, most of the zeolite continuously releases the water contained' without changing their crystal structure. In this way, they are capable of modulating other compounds, for example as catalysts or ion exchangers. In addition, zeolites exhibit a screening effect by combining molecules that are smaller than the pore size of the lattice channel system. Larger molecules are therefore excluded. In the aluminum niobate structure, the cation needs to be balanced with the negative charge of the A1CU tetrahedron. In particular, the synthesis of zeolites has been extensively described in the synthesis of zeolites, ACS Proceedings Series 398, Μ·L. Ocelli and Η·Ε· Robson (1989) 2-7. Hydrophobic zeolites having a ratio of ceria/alumina in the structure of > l, high hydrothermal stability and resistance to aqueous alkaline solutions are disclosed in the patent application DE 195 32 500 A1. These zeolites have a 6 degree degree applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) "" -Γ------------------- Order ---------Line··· (Please read the phonetic on the back? Please fill out this page again) 1282742 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printed Clothing V. Inventions ( < ) The particle size is significantly below 150 microns. The use of hydrophobic zeolites for reducing and avoiding organic odors is taught in the patent document US 4,795,482. This odor-reducing measurement is carried out using a gas chromatography method on the liquid surface. It is known from the patent applications WO 91/12029 and WO 91/12031 that the hydrophobic zeolite prepared as described in US 4,795,482 or in a similar manner can be used in combination with a superabsorbent, wherein the zeolite is essentially 』 Bonded with superabsorbent. The resulting composite can be used in health care products such as diapers or pads. The mixture was prepared by mixing the superabsorbent and zeolite under dry conditions. Water was then added and the aggregation of the particles was observed (W〇91/12031). After the drying step, the mixture can be rubbed into a hygiene product. In patent application WO 91/12029, the zeolite is co-dispersed in water with a binder and applied to the superabsorbent during the coating process, wherein the zeolite is used in an amount of at least 20% relative to the superabsorbent. . Both of these methods have their disadvantages because the bonding of the zeolite material to the polymer is very weak and the separation and delamination of the superabsorbent and zeolite occurs even when low mechanical stresses are applied to the composite. Such mechanical stresses are produced, for example, when transporting superabsorbents and/or absorbent products including superabsorbent polymers. In addition to stratification, there is also the problem of handling very fine particles. Also, when the superabsorbent is subjected to the second treatment using an aqueous dispersion which may contain a binder, it is expected that the structure of the superabsorbent and the swelling property of the resultant may be damaged. In superabsorbent composites, a high ratio of non-swelling zeolite materials represents an additional limitation on the mode of nature. 7 paper sizes in the patent applications EP 0,811,387 A1 and EP 0,811,390 A1 apply to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Ί------------- ------Set--------- line (please read the phonetic on the back? Please fill out this page again) 1282742 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Invention description (1 ;) It is known that a zeolite having a ceria/alumina ratio of from 1 to 5 can be used as an odor absorbent in a liner. The products prepared according to the above documents have been clinically tested and the products used have also been evaluated by the testers in the olfactory test panel. The dry mixture described in the above patent application is highly susceptible to delamination. In addition to this, the amount of zeolite required in the above patent application is extremely high, which is an adverse effect on the comfort when wearing a health care product. It is therefore an object of the present invention to provide a polymer capable of absorbing water and an aqueous liquid having a substance which can bond, for example, malodorous organic compounds which are secreted by urine or other fluids secreted by the body, and wherein - during use thereof Significantly reduce the release of malodorous substances into the vapor domain; - store a substantially uniform distribution of fragrance substances in the absorbent; - avoid stratification in the pre-case conditions and during use as much as possible; - absorbent under pressure Having good retention and swelling properties; and - using as low a quantity of fragrance material as possible to achieve fragrance modification. The object of the present invention is to provide a process for the manufacture of the deodorant absorbent polymer, wherein - Avoid mixing the substantially different dry substances in the particle size, such as granules and powders, and the resulting troubles; - no dust generation; and - avoiding the aggregation of particles during preparation. According to the present invention, the object is achieved by a cross-linking, monoethylenic unsaturation, partial neutralization monomer carrying an acid group to form an absorbent polymer, 8 paper scales applicable to Chinese national standards (CNS) ) A4 size (210 X 297 mm) " '~' " Ί------------------- order--------- line · ( Please read the notes on the back and fill out this page.) 1282742 A7 Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, Printed B7 V. INSTRUCTIONS (7) The polymer has a separate or mixed α,3,7,5-cyclod paste. Fine or its derivatives, and sorghum content zeolites are bonded or combined ionic, covalently or mechanically. In the meaning of the present invention, "high in silicon" means that the ratio of cerium oxide/alumina is > 1 〇, preferably > 20, more preferably > 50, and even more preferably >;1〇〇. The ratio of ceria/alumina is particularly good when it is >5〇〇. By "crosslinked" in the meaning of the present invention is meant that the polymer has been crosslinked and/or has been surface crosslinked. The zeolite used in the present invention is a dealuminized, hydrophobic (lipophilic) zeolite variant having a ceria/alumina ratio of > 10, preferably > 20, more preferably > 50, and especially good for > 100. The most preferred is the ceria/alumina ratio of > 500. The amount used is 0.0 M0% by weight, preferably 0.1 to 5% by weight, and more preferably 0.70 to 3% by weight based on the total amount of the absorbent. Such zeolites are, for example, the product Alscents® sold by Degussa AG under the trade name Flavith® or by U〇P. Flavith® identification is more detailed in the KC-CZ 42-1-05-1098 T&D product data sheet. This product data sheet is hereby incorporated by reference in its entirety for all of its disclosure. Polymers having superabsorbent properties selected in the present invention can be polymerized using various methods, such as bulk polymerization, solution polymerization, spray polymerization, inverse emulsion polymerization, and inverse dispersion polymerization. Preferably, water is used as a solvent for solution polymerization. Solution polymerization can also be carried out using continuous or batch processes. In the patent literature, the private paper scale applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm-7------------------- --- Line (please read the note on the back? Please fill out this page again) A7 1282742 ___B7___ V. Description of invention (3) Includes the concentration and temperature, the type of initiator and the second catalyst. The wide range may vary. Typical methods are described in the following patent specifications: US 4,286,082; DE 27 06 135, US 4,076,663, DE 35 03 458, DE 40 20 780, DE 42 44 548, DE 43 23 001, DE 43 33 056, DE 44 18 818. The disclosures of which are hereby incorporated by reference in its entirety, the entire disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosures of Acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, vinyl acetic acid, vinyl sulfonic acid, methallyl sulfonic acid, 2-acrylamido-2-yl Small propyl sulfonic acid, and alkali and/or ammonium salts, preferably using acrylic acid and its base and / or ammonium salts, and mixtures thereof. It is also possible to hydrolyze the monomer to an acid group at the last possible stage before the polymerization with, for example, a nitrile group. To change the polymer properties, up to 30% by weight of other comonomers can be dissolved in the aqueous polymerization batch, for example Acrylamide, methacrylamide, acrylonitrile, (meth)allyl alcohol ethoxylate, and optionally a mono(meth)acrylate of an alcohol or ethoxylate. A small amount of a crosslinking monomer of a reactive group can be copolymerized with the above-mentioned monomer, thereby forming a partially crosslinked polymerization product which is no longer soluble in water but swells. A double- or multifunctional monomer such as guanamine Such as methylene bis propylene- or - methacrylamide, or ethylene bis acrylamide can be used as a crosslinking monomer, and also an allyl compound such as allyl (meth) acrylate Preferably, the alkoxylated allyl (meth) acrylate, triallyl cyanate, diallyl maleate, 10 parts are reacted with 1 to 30 moles of oxyalkylene oxide ^Zhang scale applies Chinese National Standard (CNS) A4 specification (210 X 297 public) """""" Ί---- ---------------Book---------Line (please read the notes on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Print Economy Ministry of Intellectual Property Bureau employee consumption cooperative printed 1227742 Α7 5, invention description () polyallyl ester, tetraallyloxyethane, triallylamine, tetraallyl ethylenediamine, phosphoric acid or Allyl esters of phosphorous acid, and N-methylated compounds of crosslinkable monomers such as undeuterated such as methyl propyl amide or propylamine and ethers derived therefrom, and polyols and oxidized polyols Esters of alcohols, such as monoacrylates or triacrylates, such as butylene glycol or ethylene glycol diacrylate, polyethylene di(meth)acrylate, trimethylolpropyl triacrylate, Oxygenated (ethoxylated) dimethylolpropyl bis and triacrylates, glycerol and pentaerythritol, and preferably from 1 to 30 moles of oxygen, with from 1 to 30 moles of oxyethylene Ethyl ethoxylated glycerol and pentaerythritol acrylates and methacrylates. Preferably, an acrylate of a tris-propylamine, a polyhydric alcohol or an alkoxide thereof, and a methyl allyl alcohol acrylate or an alkoxide thereof are used. The ratio of the crosslinking monomer is from 0.01 to 3.0% by weight, preferably from 0.05 to 2.0% by weight, and most preferably from 〇5 to 5% by weight, based on the total monomers. Preferably, the acidic monomers are subjected to neutralization. Neutralization can be carried out in a variety of different ways. According to the teaching of U.S. Patent 4,654,039, the polymerization can be carried out directly on the one hand with an acidic monomer followed by neutralization in a polymer gel. This patent specification is hereby incorporated by reference herein in its entirety in its entirety in its entirety in its entirety herein in its entirety On the other hand, and preferably, the acidic monomer component is neutralized to 20 to 95%, preferably 50 to 80%, before the polymerization is carried out. In this case, when the polymerization starts, the system is It is present in the form of sodium and/or potassium salts and/or ammonium salts. It is preferred to use a base which does not have an adverse effect on the subsequent polymerization for neutralization. It is preferred to use sodium hydroxide or potassium hydroxide solution and/or ammonia, wherein the sodium hydroxide solution is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) for the paper scale J.------ ------------- Order --------- line (please read the phonetic on the back? Please fill out this page again) 1282742 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. INSTRUCTIONS () Particularly preferred; in accordance with the teachings of us 5,314,420 and US 5,154,713 'addition of sodium carbonate, potassium carbonate or sodium bicarbonate has an additional positive effect. The partially neutralized monomer solution is cooled to a temperature below 3 (TC below, preferably below 20 °C) prior to initiating polymerization of the polymerization of the adiabatic solution. These patent specifications are hereby incorporated by reference. Reference is made to a part of the disclosure. In another method mentioned, other temperatures are conventional and customary according to the teachings of the art. The polymerization product of the invention may contain up to 40% by weight of water soluble. The polymer is used as a matrix for grafting. In particular, these include partially or fully saponified polyvinyl alcohol, starch or starch derivatives, cellulose or cellulose derivatives, polyacrylic acid, polyethylene glycols, or The above mixture is added to the environment in which the molecular weight of the polymer as the grafting substrate must match the conditions of action of the polymer. For example, in the case of an aqueous solution polymerization, it may be necessary to use a low or medium molecular weight for the purpose of viscosity. Polymer, however, this factor plays only a minor role in suspension polymerization. In addition to partial neutralization of acrylic acid for cross-linking polymerization In addition to the polymer obtained, it is preferred to use a component which additionally contains graft-polymerized starch, or polyvinyl alcohol. The polymerization process of the invention can be initiated using a variety of different conditions, for example using radioactivity, electromagnetic or Irradiation with ultraviolet radiation, or redox reaction using two compounds, such as sodium bisulfite and potassium persulfate, or ascorbic acid and hydrogen peroxide. It can also be used as a polymerization initiator. The initiator of the action is thermally induced to decompose. The radical initiators are, for example, azobisisobutyronitrile, sodium pyrosulfate peroxide, and the 12th paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X). 297 mm) J-------------------- order--------- line (please read the notes on the back and fill out this page) 1282742 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Print A7 B7 V. Invention Description (丨丨) Tributyl hydroperoxide, or benzoyl peroxide. In addition, a combination of the above methods can also be used. These polymerization products can be prepared according to the following two methods According to the first method, partially neutralized acrylic acid is converted into a gel by radical polymerization in an aqueous solution with a crosslinking agent and a polymer additive, and then the gel is crushed and Dry until powdered, flowable, honed and screened to the required particle size. Solution polymerization can be carried out in continuous or batch mode. Included in the patent literature with concentration conditions, temperature, initiation A wide range of variability in the type and amount of the agent, and the variability in the second cross-linking. Typical methods are described in the following patent specifications: US 4,076,663; US 4,286,082; DE 27 06 135, DE 35 03 458, DE 35 44 770, DE 40 20 780, DE 42 44 548, DE 43 23 0 (U, DE 43 33 056, DE 44 18 818. These documents are hereby incorporated by reference in their entirety for all of the disclosures. A method of reverse suspension and emulsion polymerization can also be used to prepare the polymerization product. In these methods, an aqueous, partially neutralized acrylic acid solution is dispersed in a hydrophobic organic solvent using a protective colloid and/or an emulsifier, and a polymerization initiator is used to initiate polymerization. The cross-linking agent may be dissolved in the monomer solution and added together after the measurement, or separately added, and optionally added subsequently. The selectively present polymeric graft matrix is either added to the monomer solution or placed directly into the oil phase. Thereafter, water is removed from the mixture by azeotropy, and the polymerized product is filtered and selectively crushed, and dried to achieve pulverization, flow dynamics, honing and screening to the desired particle size. 13 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) I--------------------tT-------- -^· (Please read the notes on the back and fill out this page.) Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumers Co., Ltd. Printed 1284742 A7 B7 V. Invention Description (\〆) The following surface crosslinking method can be used to improve the present invention. The nature of the polymerization product, especially the liquid absorption under pressure, thus avoiding the "gel blocking" phenomenon in which the slightly swollen polymer particles adhere to each other, whereby, for example, diapers Prevent further liquid absorption and liquid distribution. In this second crosslinking, a crosslinking agent can be used to crosslink the carboxyl groups of the polymer molecules at the surface of the superabsorbent particles at an elevated temperature. The second method of cross-linking has been described in several patent specifications, such as DE 40 20 780, EP 317,106 and W0 94/9043. In accordance with the present invention, all of the second cross-linking agents disclosed in U.S. Patent No. 5,314,420, the disclosure of the entire disclosure of The combination. The above-cited documents are hereby incorporated by reference herein in its entirety by reference in its entirety herein in its entirety. Typically, these compounds contain at least two functional groups sufficient to react with the carboxylic acid or carboxyl group. Alcohol, amine, aldehyde, and carbonate groups are preferred, and crosslinker molecules having different functionalities can also be used. Preferred are polyols, polyamines, polyamino alcohols, polyepoxides, and alkylene carbonates. In particular, the following second crosslinking agent can be used: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, polyglycerol, propylene glycol, diethanolamine, triethanolamine, polypropylene glycol 'epoxy Block copolymer of ethane and propylene oxide, sorbitan fatty acid ester, sorbitan fatty acid ester, trimethylolpropane, ethoxylated trimethylolpropane, pentaerythritol, pentaerythritol ethoxylate, polyvinyl alcohol 'sorbitol' ethylene carbonate, propylene carbonate. Particularly preferred is the use of a polyol and ethylene carbonate as a second crosslinking agent. The amount of the second crosslinking agent used is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) relative to the paper size of the polymer to be subjected to the second crosslinking. -------------- Order --------- line (please read the note on the back and then fill out this page) 1282742 A7 _____B7_____ V. Invention Description (Ο) 0.01 to 30% by weight, preferably 0.1 to 10% by weight. (Please read the note on the back? Please fill out this page again.) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperatives print before the second cross-linking effect, preferably dry polymer first, honing, in the applied technology The individual particle fractions required are screened and then placed into a second cross-linking reaction. However, it has been demonstrated that in some cases it may be advantageous to add a second crosslinking agent prior to drying the polymer gel, or at an earlier stage prior to honing the partially or completely dried polymer. The second cross-linking effect used in the present invention has been disclosed in U.S. Patent No. 4,666,983 and DE 40 20 780. These documents are hereby incorporated by reference in their entirety for all of the disclosure. It is advantageous for these second crosslinkers to be added as a solution of water, an organic solvent or a mixture of the above, especially in these cases where a low amount of a second crosslinker is used. Suitable mixing devices for applying the second crosslinking agent are, for example, Patterson-Kelley mixers, DRAIS turbulent mixers, L5 dige mixers, Ruberg mixers, spiral mixers, turntable mixers, and fluid-bed mixers, and A continuously operated vertical mixer (Schugi mixer) that mixes powder at a high frequency using a rotary knife. Once the second crosslinking agent is mixed with the pre-crosslinked polymer, it is heated to a temperature of 60 to 250 ° C, preferably 135 to 200 ° C, and more preferably 150 to 185 ° C, so that it can be carried out The second crosslinking reaction. The time period of additional heating is limited by the time when the property pattern required for the polymerization product is destroyed by thermal damage. Depending on the type used, it can be treated with a variety of different screening grades, such as between 100 and 1 micron, and preferably between 150 and 850 microns for diapers. In general, this particle grading is applied before and/or after the second cross-linking, using the Chinese National Standard (CNS) A4 specification (210 X 297 mm) using honing and laying 15 paper scales. 1282742 A7 B7 Description of the invention - breaking, followed by drying, honing; - selective screening; and - surface crosslinking; wherein the high cerium content zeolite is added to the polymerization product during the final surface crosslinking. Preferably, the addition of high cerium content zeolite is in suspension. In the meaning of the present invention, "high strontium content" means that the ratio of cerium oxide/aluminum oxide is > 10, preferably > 20, more preferably > 50, and even more preferably > The ratio of ceria/alumina is > 500 is particularly preferred 〇 The zeolite used is in suspension. The preferred liquid phase is water, but a mixture of water and an organic solvent can also be used. In accordance with the present invention, the addition of zeolite can be carried out in various stages of the manufacture of the powdered polymeric product as described hereinafter. The zeolite in the aqueous suspension can be added to the polymerization product before or during the preparation process, so that a particularly effective bond can be achieved between the odor absorption component and the polymerization product. In a preferred embodiment of the process of the invention, the zeolite is added directly to the aqueous monomer solution prior to polymerization. When the absorbent is produced in the suspension polymerization, it is also possible to precharge all or part of the zeolite in the oil phase and measure the monomer solution. When only a portion of the zeolite is precharged, the remainder can be added by means of a monomer solution. In another preferred embodiment of the process of the invention, the zeolite is applied to the crushed paper in the form of a suspension in water or an organic solvent or a mixture of the two. The paper is of the Chinese National Standard (CNS) A4 specification (210 X). 297 mm) (Please read the notes on the back and fill out this page) ---------Book -------- Line" Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1282742 A7 Economy Ministry of Intellectual Property Bureau employee consumption cooperative printed B7 V. Inventive Note (\r[) According to the present invention, the water content needs to be reduced to less than 10% by weight before the addition of the high cerium content zeolite. Preferably, the water content is reduced to less than 30% by weight, more preferably not less than 50% by weight 'and even more preferably not less than 65% by weight, prior to the addition of the high sand content zeolite. It is preferred to use a suspension when the zeolite is added to the polymerization product. When using the process of the invention 'When zeolite enthalpy to synthetic polymer can produce absorbent polymer, even after applying mechanical stress', for example 6 minutes in a 95 rpm ball mill, the zeolite is not completely removed from the polymerization product. . In the process of the present invention, after such stress is applied, less than 80%, and usually 40-60%, the total amount of zeolite in the polymerization product is removed. The polymerized product of the present invention exhibits improved absorbability to malodorous compounds as compared to a powdered absorbent which does not contain zeolite. Among the polymerization products, when found in, for example, health care products and can absorb body fluids such as urine, or packaging fields such as meat and fish products, they can utilize swelling and form hydrogels to absorb large amounts of aqueous liquids and body fluids, For example, urine, blood, or gravy. Therefore, the present invention also relates to such use. The polymerized product of the present invention can be used as a powder structure to absorb a liquid or previously fixed in a foamed or unfoamed sheet material. For example, the structure for absorbing liquid is an diaper for an infant, an incontinence article, or an absorbent placed in a package in a food. In the absorbent polymerization product of the present invention, the bonding force of the zeolite to the polymer is extremely strong even under mechanical stress, for example, transporting the absorbent polymerization product, so that the polymer and the zeolite do not produce 19 sheets of paper. Scale _ + @国标准(CNS)A4 Specification (21G X 297 公爱) ^-------------------Book---------Line ( Please read the phonetic transcription on the back? Please fill out this page.) 1282742 A7 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed Β7 V. Invention Description (0) Separation and stratification of the substance 'and in particular does not produce extremely fine The problem with particles. Further processing of the polymeric product of the present invention is advantageous because, according to the foregoing, separation and homogeneous dosing of the superabsorbent and zeolite, particularly small amounts of zeolite, are not achieved. The polymeric product of the present invention can be readily formulated to provide a polymeric product and a fragrance component having a certain concentration of superabsorbent properties in the absorbent product. Furthermore, it has been found that the absorbent of the present invention is particularly excellent for intrusion into an active substance. The stability of the sensitive active substance', e.g., associated with oxidative degradation, can be substantially improved upon exposure to the absorbent of the present invention. Further, the polymerization product of the present invention can be used for plant cultivation and for controlling pests in agriculture. In terms of plant cultivation, the polymerization product adjacent to the root of the plant can sufficiently supply the liquid and the nutrients added in advance, and it can be simultaneously stored and released over an extended period of time. In terms of pest control, the polymerization product may be added to a single active substance or a combination of multiple active substances' which is used for release in a time and quantity controlled manner. The invention will be illustrated in the following examples. However, these examples are merely illustrative of the invention and are not intended to limit the general inventive concept. The manufacture and properties of the polymeric products of the present invention are explained below. In addition, methods and procedures for determining the properties of polymers having superabsorbent properties will also be described. Test Method Test Method 1: Determine the retention by using the tea bag method, and apply the Chinese National Standard (CNS) A4 specification (210 X 297 public) for three paper measurements. I----------- ----------IT---------^· (Please read the note on the back? Please fill out this page again) 1282742 A7 B7 V. Invention Description ο/) (Please first Read the note on the back and fill out this page). Approximately 200 mg of the polymerized product was added to a tea bag and immersed in a 〇.9% NaCl solution for 30 minutes. The tea bag was then centrifuged in a centrifuge (23 cm in diameter, 1400 rpm) for 3 minutes and weighed. A tea bag containing no water absorbing polymer was used as a blank test. Retention = final weight - blank experiment / starting weight [g / g] Test Method 2: Liquid Absorbency under Pressure (AAP Test, EP 0,339,461) Absorbent System under Pressure (pressure Load 50 g/cm2) It was determined according to the method described in EP 0,339,461, page 7. This document is hereby incorporated by reference in its entirety in its entirety herein in its entirety herein in its entirety in its entirety. Approximately 0.9 grams of the superabsorbent was placed in a cylinder with a bottom of the screen and weighed. The evenly distributed superabsorbent layer was loaded with a piston that released a pressure of 50 g/cm2. The pre-weighed cylinders were then placed on a glass filter plate and placed in a shallow pan containing 〇.9% NaCl solution. The height of the filter plates was the same. After the cylinder unit absorbs 0.9% NaCl solution for 1 hour, it is re-weighed and the AAP is calculated according to the following: Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing clothing AAP=final weight (cylinder unit + superabsorbent) Weight (Cylinder unit + superabsorbent after impregnation) / Initial weight test method for superabsorbent 3: Determination of absorbency of malodorous compound 1 1 g of powdery absorbent added to 2 ml of aqueous solution of malodorous compound (including 5 weight % ethanol) and sealed in a 5 ml test container. It was placed at 23 ° C for 12 hours, and the level of the malodorous compound in the vapor field on the liquid was quantitatively measured with respect to a blank test using a head space GC. Test Method 4: Determination of bismuth content of absorbent polymer by applying bismuth citrate 21 paper size to China National Standard (CNS) A4 specification (210 X 297 mm) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1282742 Δ7 Α7 Β7 V. Description of the invention (y°) Reaction into molybdenum blue followed by photometric analysis. In advance, hydrazine has been used to quantify the reaction to form sulphate using alkali decomposition (Photometrische Analyse, ed.: Lange Lange, Zdenek L, Vejdelek S., 1987 edition, page 383, VCH). EXAMPLES: Example la This example illustrates the preparation of a polymer gel having superabsorbent properties. Prepare 1300 g of acrylic acid, 2115.9 g of distilled water, 2.7 g of polyacrylic acid ethylene glycol monoallyl ether ester, and 1.25 g of a polyethylene glycol diacrylate solution. Using 899.10 g of a 50% sodium hydroxide solution, partial neutralization (degree of neutralization (DN): 60%) was carried out by stirring, and cooling was carried out. The solution was cooled to 7-8 ° C and ventilated with nitrogen for approximately 20 minutes. Then, 0.45 g of azobis(2-amidinopropane) dihydrochloride dissolved in 22.5 g of distilled water, 1.35 g of sodium peroxodisulfate dissolved in 25 g of distilled water, and dissolved in 22.5 g of distilled water were added. 0.315 grams of hydrogen peroxide (35%). Later, the polymerization was initiated by the addition of 0.0675 g of ascorbic acid dissolved in 9 g of water, during which the temperature was significantly increased. A gel-like product is obtained, and further processing will be described in the examples below. EXAMPLE lb This example illustrates the preparation of another polymer gel having superabsorbent properties. Prepare 1300 g of acrylic acid, 2015.9 g of distilled water, 6.5 g of polyacrylic acid ethylene glycol monoallyl ether ester, and 3.9 g of polyethylene glycol diacrylate solution. Use 997.10g of 50% sodium hydroxide solution 'Using the agitating 22 *5^ scale to apply the Chinese National Standard (CNS) A4 specification (210 χ 297 mm ^ I---------------- ----Book---------Line 41^ (Please read the note on the back and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1227442 A7 B7 V. Invention Description (> 4) Mix and carry out partial neutralization (DN=70%), cool. The solution is cooled to 7-8 °C and ventilated with nitrogen for about 20 minutes. Then, 0.45 g of azo double dissolved in 22.5 g of distilled water is added. (2-amidinopropane) dihydrochloride, 1.35 g of sodium peroxodisulfate dissolved in 25 g of distilled water, and 0.315 g of hydrogen peroxide (35%) dissolved in 22.5 g of distilled water. Starting by the addition of 0.0675 grams of ascorbic acid dissolved in 9 grams of water, the temperature during which it is produced is significantly increased. A gel-like product is obtained, and further processing will be described in the examples below. Example lc Prepare another polymer gel with superabsorbent properties. Prepare 1300 grams of acrylic acid, 2017.19 grams of distilled water, As a cross-linking agent, 3.9 g of triallylamine solution. Using 997.10 g of 50% sodium hydroxide solution, partial neutralization (DN = 70%) was carried out by stirring, and the solution was cooled to 7-8 ° C. The gas was ventilated for about 20 minutes. Then, 0.45 g of azobis(2-fatylpropane) dihydrochloride dissolved in 22.5 g of distilled water was added, and L35 g of sodium peroxodisulfate dissolved in 25 g of distilled water was added. And 0.315 g of hydrogen peroxide (35 %) dissolved in 22.5 g of distilled water. Thereafter, the polymerization was initiated by adding 0.0675 g of ascorbic acid dissolved in 9 g of water, during which the temperature was significantly increased. The product, further processing, will be described in the examples below. Example 2 500 grams of the gel from Example lb-c was broken up and sprinkled evenly over the amount of Flavic® according to the quantities shown in the table below. S108 (Degussa AG, 23 (please read the note on the back and fill out this page) ----11--Book---II--I A paper scale applies to China National Standard (CNS) A4 specification (210 χ 297 mm) Example Retention [g/g] Flavith S108 wt.-% Flavith D wt-% Zeolite A wt.-% 2a 32.5* 1 0 0 2b 32.5* 2 0 0 2c 33.0* 0 1 0 2d 33.0* 0 2 0 2e* 31.0# 0 0 1 2f** 30.8# 0 0 2 1282742 A7 B7 V. Description of the invention (〆)
Si〇2/Al2〇3 比率約爲 500 )或 Flavith® D (Degussa AG， Si〇2/Ah〇3比率約爲56)或沸石A (Si〇2/Al2〇3比率<5)在 水中的懸浮液，後來在15〇°C之循環空氣烘箱中乾燥至殘 餘水含量爲<10%。因爲所使用之沸石A並非爲高砂含量 沸石，實施例e和f做爲比較實施例。 _ι *得自於比較實施例lb之水凝膠 #得自於比較實施例lc之水凝膠 **比較實施例 實施例3 在這個實施例中，具有超吸收劑性質之聚合產物在未 存有沸石時，檢測在壓力下的滯留性和液體吸收性。 得自於實施例la-c之50克經乾燥及硏磨的聚合物經 篩選成爲150-850微米，在一個塑膠容器中以0.5克碳酸亞 乙基酯和1.5克水濕潤，使用商用的家庭式手提攪拌器（ Krups公司）劇烈攪拌且完全混合。接著，經濕潤的聚合 物在溫度爲180°C的烘箱中加熱30分鐘。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） »--------------------訂---------線· ··_ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 實施例 滯留性[g/g] AAP [g/g] 3a 32.0 22.5 3 b 28.0 24.5 3c 27.0 23.5 24 實施例 滯留性[g/g] AAP [g/g] 4a 27.5 24.5 4b 27.5 24.5 4c 28.0 24.0 4d 27.5 24.0 氺木 27 23.5 4f** 26.5 23.5 1282742 A7 B7 五、發明說明（ 7》） 實施例4 在這個實施例中，在加入沸石後進行表面交聯作用。 得自於實施例2a-f之50克經乾燥及硏磨的聚合物經 篩選成爲150-850微米，在一個塑膠容器中分別以碳酸亞 乙基酯（EC)和水濕潤，使用商用的家庭式手提攪拌器（ Krups公司）劇烈攪拌且完全混合。該溶液爲每1.8克水含 有0.25克EC。接著，經濕潤的聚合物在溫度爲170°C的烘 箱中加熱30分鐘。 **比較實施例 實施例5 在這個實施例中，沸石係在進行表面交聯作用期間加 入。 將得自於實施例la之50克經打碎，乾燥及硏磨的聚 合物篩選成爲150-850微米，在一個塑膠容器中分別以 0.25克碳酸亞乙基酯（EC)和1.8克水，及依據在下表中 所示數量的Flavith® S108 (Degussa AG)懸浮液（所示之 乾燥物質％爲相對於丙烯酸）濕潤，使用商用的家庭式手 提攪拌器（Krups公司）劇烈攪拌且完全混合。接著，經 濕潤的聚合物在溫度爲18〇°C的烘箱中加熱30分鐘。 25 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------------------訂---------線 (請先閱讀背面之注音？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 1282742 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明 實施例 滯留性[g/g] AAP [g/g] Flavith S108 wt.-% 5a 30.6 22.5 1 5b 29.7 21.8 2 由此顯然可知，相較於實施例3，所得之壓力下滯留 性或液體吸收性僅在測量準確度範圍之內稍微改變。 比較實施例3a (類似於WO 91/12029) 10克之甲基纖維素（Walocel VP-M 20678)使用高速 率混合器而分散於40克Flavith® S108和190克水中，後來 利用實驗用混合器混合入50克商用超吸收體（售自 Stockhausen 公司的 Favor® SXM 6860)，及在 60°C 下，於固 定氣流中的流體床乾燥機乾燥20分鐘。 比較實施例3b (類似於WO 91/12029) 0.25克之甲基纖維素（Walocel VP-M 20678 )使用高 速率混合器而分散於1克Flavith® S108和5克水中，後來 利用實驗用混合器混合入50克商用超吸收體（售自 Stockhausen 公司的 Favor® SXM 6860)，及在 60°C 下，於固 定氣流中的流體床乾燥機乾燥20分鐘。 名稱 TB[g/g] AAP [g/g] C3a 20.5 9.0 C3b 29.0 18.4 SXM 6860 31.0 24.0 相較於SXM 6860，除了顯著的劣化情形之外，特別 是在壓力下的吸收能力，該複合材料的不穩定性在混合或 運輸該材料時的重度形成粉塵即明顯看出。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------------------訂---------^ AW (請先閱讀背面之注意事項再填寫本頁) 1282742 A7 _B7__ 五、發明說明（/ ) 比較實施例4 在此實施例中，沸石在進行表面交聯作用之後加入。 得自於實施例3中之50克產物與依據在下表中所示 數量的沸石（Flavith® S108，售自Degussa-Hiils公司）在水 中的懸浮液完全混合而灑佈其中。該產物在烘箱中乾燥至 殘餘的水含量爲<4%。 I------------------tr--------線· (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 27 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 1282742 _ B7 五、發明說明（/U) 名稱 Flavith S108[%] C4a 2 C4b 1 實施例6 篩選得自於比較實施例3和4的產物，及使用具有 150-850微米粒度大小之顆料進行球磨機穩定性測試，其中 產物在95 rpm之球磨機中施加應力6分鐘。同樣地，得自 於實施例2b的產物亦進行相同的球磨機穩定性測試。再次 地，篩選該等產物，及使用具有<150微米粒度大小之顆 料依據測試方法4檢測其矽含量。當所使用的沸石之顆粒 大小顯著地低於150微米時，可使用這個方法測試在具有 超吸收劑性質聚合物中鍵結或倂入的沸石數量。下列相對 於總乾燥物質之矽數量係見於各試樣中: --------------------訂---------線 ** (請先閱讀背面之注意事項再填寫本頁) 得自各實施例之產物 球磨機 測試 SiCb 含 量[%] Si〇2含量理 論値1[%] 依據 W0 91/12031 實 施例12之比較實施例 是 5.2 2 比較實施例C3a 否 79.9 40 比較實施例C3a 是 79.1 40 比較實施例C3b 否 5.3 2 比較實施例C3b 是 3.2 2 2b 是 1.7 2 比較實施例C4a 是 2.9 2 經濟部智慧財產局員工消費合作社印製 1 相對於本發明中具有超吸收劑性質聚合物之總數量 2 50克之SAP(售自Stockhausen公司的超吸收體；FAVOR® SXM 6860)和與1克之Flavith® S108利用Krups公司的厨房 式混合器混合。加入15克水之後，可觀察到該物質之聚集 作用。在60°C下乾燥120分鐘。 由此顯然可知，相較於前案所製備而得之產物，本發 28 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1282742 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（yy) 明中微粒<150微米之產物具有較低的矽，g此証實本發 明產物中沸石對聚合物具有更強的鍵結力。同樣地，依據 W〇91/12029及WO 91/12031而製得之複合材料相較於本發 明之產物爲更顯著地不穩定，此可由進行球磨機穩定性試 驗之前與之後所增加之Si〇2含量來証實。更特而言之，顯 然可知者爲，因爲高百分率之疏水性沸石在製備之後仍與 超吸收體物質分離，前案之方法並無法有效地鍵結如此高 數量的沸石。當該材料施加機械應力時，大量沸石另又移 出，其証實係爲在球磨機中施加壓力之後細微粉塵中的高 二氧化矽含量。比較實施例C4a示範出，即使使用少量的 沸石(2%)，前案方法中的鍵結力相較於本發明方法(實施例 2b)仍是顯著地差。 實施例7 這個實施例係爲檢測惡臭化合物蒸氣域濃度的降低。 在度量惡臭物質中，依據測試步驟2，檢測不具有沸 石的聚合物做爲空白試驗，及所測得的惡臭物質蒸氣域濃 度設定爲100%。後來，檢測含有沸石的試樣，並檢測惡 臭物質的蒸氣域濃度。圖中的右欄係依下列計算：100 X ( 由含沸石之聚合物測得之異味物質數量/由未含沸石之聚 合物測得之異味物質數量）。 29 $紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------訂---------線 4 ^ (請先閱讀背面之注咅？事項再填寫本頁) 1282742 A7 B7Si〇2/Al2〇3 ratio is about 500) or Flavic® D (Degussa AG, Si〇2/Ah〇3 ratio is about 56) or zeolite A (Si〇2/Al2〇3 ratio <5) in water The suspension was then dried in a circulating air oven at 15 ° C until the residual water content was < 10%. Since zeolite A used was not a high sand content zeolite, Examples e and f were used as comparative examples. _ι * Hydrogel obtained from Comparative Example lb #Hydrogel obtained from Comparative Example lc **Comparative Example Example 3 In this example, the polymerization product having superabsorbent properties was not present When zeolite is present, retention under pressure and liquid absorption are measured. 50 grams of the dried and honed polymer from Example la-c was screened to 150-850 microns, wetted with 0.5 grams of ethylene carbonate and 1.5 grams of water in a plastic container, using a commercial household The hand blender (Krups) was stirred vigorously and thoroughly mixed. Next, the wet polymer was heated in an oven at a temperature of 180 ° C for 30 minutes. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) »-------------------- Order--------- Line · ··_ (Please read the note on the back and fill out this page) Department of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Example Retention [g/g] AAP [g/g] 3a 32.0 22.5 3 b 28.0 24.5 3c 27.0 23.5 24 Example retention [g/g] AAP [g/g] 4a 27.5 24.5 4b 27.5 24.5 4c 28.0 24.0 4d 27.5 24.0 Eucalyptus 27 23.5 4f** 26.5 23.5 1282742 A7 B7 V. Description of invention (7) Example 4 In this example, surface crosslinking was carried out after the addition of zeolite. 50 grams of the dried and honed polymer from Examples 2a-f were screened to 150-850 microns, wetted with ethylene carbonate (EC) and water in a plastic container, using a commercial household The hand blender (Krups) was stirred vigorously and thoroughly mixed. The solution contained 0.25 grams of EC per 1.8 grams of water. Next, the wet polymer was heated in an oven at a temperature of 170 ° C for 30 minutes. **Comparative Example Example 5 In this example, the zeolite was added during surface crosslinking. 50 grams of the crushed, dried and honed polymer from Example la was sieved to 150-850 microns, with 0.25 grams of ethylene carbonate (EC) and 1.8 grams of water in a plastic container, respectively. And according to the amount of the Flavith® S108 (Degussa AG) suspension shown in the table below (the % of dry matter shown is relative to acrylic acid), it was vigorously stirred and thoroughly mixed using a commercial household hand blender (Krups). Next, the wet polymer was heated in an oven at a temperature of 18 ° C for 30 minutes. 25 The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --------------------- Order -------- - Line (please read the phonetic transcription on the back? Please fill out this page again) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1227742 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description Example retention [g/ g] AAP [g/g] Flavith S108 wt.-% 5a 30.6 22.5 1 5b 29.7 21.8 2 It is apparent from this that the resulting pressure retention or liquid absorption is only in the measurement accuracy range compared to Example 3. Changed slightly within. Comparative Example 3a (similar to WO 91/12029) 10 grams of methylcellulose (Walocel VP-M 20678) was dispersed in 40 grams of Flavieth® S108 and 190 grams of water using a high rate mixer, which was later mixed using an experimental mixer. 50 grams of commercial superabsorbent (Favor® SXM 6860 from Stockhausen) was placed and dried at 60 ° C for 20 minutes in a fluid bed dryer in a fixed gas stream. Comparative Example 3b (similar to WO 91/12029) 0.25 grams of methylcellulose (Walocel VP-M 20678) was dispersed in 1 gram of Flavith® S108 and 5 grams of water using a high rate mixer and later mixed using an experimental mixer 50 grams of commercial superabsorbent (Favor® SXM 6860 from Stockhausen) was placed and dried at 60 ° C for 20 minutes in a fluid bed dryer in a fixed gas stream. Designation TB[g/g] AAP [g/g] C3a 20.5 9.0 C3b 29.0 18.4 SXM 6860 31.0 24.0 In contrast to SXM 6860, in addition to significant degradation, especially under pressure, the composite The instability is evident when the dust is heavily formed when mixing or transporting the material. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) --------------------- Order --------- ^ AW (Please read the note on the back and then fill out this page) 1282742 A7_B7__ V. INSTRUCTIONS (/) Comparative Example 4 In this example, the zeolite was added after surface crosslinking. 50 g of the product from Example 3 was sprinkled with a suspension of water in accordance with the amount of zeolite (Flavith® S108, available from Degussa-Hiils) as shown in the table below. The product was dried in an oven to a residual water content of < 4%. I------------------tr--------Line· (Please read the notes on the back and then fill out this page) Ministry of Economic Affairs Intellectual Property Office staff consumption Co-operative printing 27 paper size applicable to China National Standard (CNS) A4 specification (210 X 297 mm) A7 1282742 _ B7 V. Invention description (/U) Name Flavith S108 [%] C4a 2 C4b 1 Example 6 Screening The ball mill stability test was carried out from the products of Comparative Examples 3 and 4 and using pellets having a particle size of 150-850 microns, wherein the product was subjected to a stress in a 95 rpm ball mill for 6 minutes. Similarly, the product from Example 2b was also subjected to the same ball mill stability test. Again, the products were screened and the ruthenium content was determined according to Test Method 4 using a particle having a particle size of <150 micron. When the particle size of the zeolite used is significantly below 150 microns, this method can be used to test the amount of zeolite bound or intrusive in a polymer having superabsorbent properties. The following quantities relative to the total dry matter are found in each sample: -------------------- Order --------- Line** ( Please read the precautions on the back and fill out this page.) The product ball mill from each example is tested for SiCb content [%] Si〇2 content theory 値 1 [%] According to W0 91/12031 The comparative example of Example 12 is 5.2 2 Comparative Example C3a No 79.9 40 Comparative Example C3a is 79.1 40 Comparative Example C3b No 5.3 2 Comparative Example C3b is 3.2 2 2b is 1.7 2 Comparative Example C4a is 2.9 2 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Print 1 SAP (a superabsorbent from Stockhausen, FAVOR® SXM 6860) and a 1 gram of Flavith® S108 are mixed with a Krups kitchen mixer in relation to the total amount of superabsorbent polymer in the present invention of 2 50 g. . The aggregation of the substance was observed after the addition of 15 g of water. Dry at 60 ° C for 120 minutes. Obviously, it can be seen that compared with the products prepared in the previous case, the paper size of this paper applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1282742 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. INSTRUCTION DESCRIPTION (yy) The fine particles < 150 micron product of the invention have a lower enthalpy, which confirms that the zeolite in the product of the invention has a stronger bonding force to the polymer. Similarly, the composites made according to W〇91/12029 and WO 91/12031 are more significantly unstable than the products of the present invention, which can be increased by Si〇2 before and after the ball mill stability test. The content is confirmed. More specifically, it is apparent that since a high percentage of hydrophobic zeolite is still separated from the superabsorbent material after preparation, the previously described method does not effectively bond such a high amount of zeolite. When the material was subjected to mechanical stress, a large amount of zeolite was removed again, which was confirmed to be the high cerium oxide content in the fine dust after the pressure was applied in the ball mill. Comparative Example C4a demonstrates that even with a small amount of zeolite (2%), the bonding force in the prior method is significantly worse than the method of the present invention (Example 2b). Example 7 This example is to detect a decrease in the concentration of the malodorous compound vapor domain. In the measurement of the malodorous substance, according to Test Step 2, the polymer having no zeolite was detected as a blank test, and the measured malodorous substance vapor domain concentration was set to 100%. Subsequently, a sample containing zeolite was detected, and the vapor domain concentration of the malodorous substance was detected. The right column in the figure is calculated as follows: 100 X (number of odorous substances measured by zeolite-containing polymer / amount of odorous substance measured by polymer not containing zeolite). 29 $paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -------------------- Order --------- Line 4 ^ (Please read the note on the back first? Then fill out this page) 1282742 A7 B7
I 五、發明說明（>多） 添加糠基硫醇及乙基呋喃： 得自實施例 的聚合物 在蒸氣域中糠基硫 醇濃度的降低率[%] 在蒸氣域中乙基呋 喃濃度的降低率[%] 4a 69.0 82.0 4b 89.0 93.0 4c 40 -- 4d 66 -- 4e 降低率< 5% 降低率< 5% 4f 降低率< 5% 降低率< 5% 5g 91.9 -- 5h 99.1 -- -未測量 本發明的吸收劑聚合產物對惡臭物質顯示顯著的降低 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 如同於比較實施例中所示者，具有低的二氧化矽/氧 化鋁比率的沸石在惡臭物質蒸氣域濃度中並無法達到令人 滿意的降低率。 爲了額外證實，由Stockhausen公司所售之FAVOR®商 用超吸收體與2重量％之具有SiCh/AhCb比率<5之各種不 同親水性沸石(A，P，X)完全混合，檢測惡臭物質之降低率 〇 相較於未含有沸石的試樣，在試樣上方蒸氣域中的惡 臭物質濃度未發現有所降低。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------訂---------線一I. Description of the invention (> multi) Addition of mercapto mercaptan and ethylfuran: reduction rate of mercapto mercaptan concentration in the vapor domain from the polymer obtained in the example [%] ethyl furan concentration in the vapor domain Reduction rate [%] 4a 69.0 82.0 4b 89.0 93.0 4c 40 -- 4d 66 -- 4e reduction rate < 5% reduction rate < 5% 4f reduction rate < 5% reduction rate < 5% 5g 91.9 -- 5h 99.1 -- - The absorbent polymer product of the present invention was not measured to show a significant decrease in malodorous substances (please read the back note first and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed as in the comparative example As shown, zeolites having a low ceria/alumina ratio do not achieve a satisfactory reduction in malodorous material vapor domain concentration. For additional confirmation, the FAVOR® commercial superabsorbent sold by Stockhausen was completely mixed with 2% by weight of various hydrophilic zeolites (A, P, X) having a SiCh/AhCb ratio < 5 to detect a decrease in malodorous substances. The rate of malodorous substances in the vapor domain above the sample was not found to be lower than that of the sample containing no zeolite. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) --------- order---------line one